CA1176395A - Polyoxymethylene fibrids, a process for their production and their use - Google Patents
Polyoxymethylene fibrids, a process for their production and their useInfo
- Publication number
- CA1176395A CA1176395A CA000365227A CA365227A CA1176395A CA 1176395 A CA1176395 A CA 1176395A CA 000365227 A CA000365227 A CA 000365227A CA 365227 A CA365227 A CA 365227A CA 1176395 A CA1176395 A CA 1176395A
- Authority
- CA
- Canada
- Prior art keywords
- polyoxymethylene
- fibrids
- weight
- fibrid
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
- C08G2/22—Copolymerisation of aldehydes or ketones with epoxy compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/11—Flash-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
- D21H5/20—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2978—Surface characteristic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Paper (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Abstract The invention relates to polyoxymethylene fibrids with a reduced specific viscosity of 0.4 to 2.0 dl/g-1, a specific surface area of 50 to 200 m2/g and a freeness of 30 to 80°SR.
According to the inyention, the fibrids are produced by flash-evaporation of a superheated solution of the polymer, a mixture of 50 - 95 % by weight of a lower alcohol with 1-4 C atoms and 5- 50 % by weight of water being used as the solvent.
The fibrids thus obtained are suitable for the production of paper.
According to the inyention, the fibrids are produced by flash-evaporation of a superheated solution of the polymer, a mixture of 50 - 95 % by weight of a lower alcohol with 1-4 C atoms and 5- 50 % by weight of water being used as the solvent.
The fibrids thus obtained are suitable for the production of paper.
Description
~7~
By fibrids there are lmderstood small fibers hich are orientated in the longitudinal direction and have a cellulose-like structure, that is to say a finite but non-uniform length, an irregular density, a fissured sur~ace and a high degree of branching. As a result of'their structure, they are particularly suitable, inter alia, for the production of paper.
m e production of such fibrids is described 9 for example, in German Patent Specification 1,290,040. In this procedure, plexus filaments are first produced and are then cut into staple lengths, the staple fiber par-ticles are suspended in a liquid and the particles in suspension are shredded in a manner which is in itself Xnown. In this context, the term plexus filaments relates to a filament-like product of a crystalline plas-tic with a three-dimensional net~rork, which is virtually free from tunnel-like channels and hollow spaces, of numerous molecular orientated ~ilm-like or sliver-like ~ibrids which are less than 2 ~ thick,are combinedwith one another and separate frorn one another along their length at irregular intervals and are preferably orientated in the direc-tion of the longitudinal axis.
These plexus filarnents and their production are described in more detail in Belgian Patent Specification 568,524.To produce theplexus filaments,asolution of a synthetic polymer under il;s autogenous pressure or under a higher pressure is extruded, at a temperature above the boiling point of t~e solvent under normal pressure, through an ~rifice into a chamber which is under a lower pressure This produotion of plexus filaments is also called flash-spiIming or expansion-spinning.
Ple~us filamen-ts can also be prepared from poly-oxymethylene by this route, and then be shredded to ~ibrids. In Belgian Patent Specifica-tion 568,524, aprotic solvents, and in particular methylene chloride, ethylene chloride, acetonitrile and methyl ethyl ketone, are used as solvents for the production of the plexus filaments. As experimen-ts have shown, no fibrids, but exclusively plexus filaments,are formed even at extremely low polymer concentrations, for example of 1 % by weight in methyl ethyl ke-tone. Since plexus filaments are unsuitable for the production of paper, according to -the abovementioned ~erman Patent Specification 1,290,040 they must be processed to fibrids in a second process step, and as a result the process becomes expensive. The :~ polyoxyme-thylene fibrids thus obtained have, in particu-lar, a relatively low specific surface area and a low freeness and the paper produced therefrom is of relatively low strength.
Fibrous products are likewise obtained on preci-pitation of polyoxyme-thylene from its solutions by super-cooling the solution or by discharging into a precipitat-. .
ing agent (compare German Auslegeschrift 1,241,116).However, paper with satisfactory proper-ties cannot be prepared therefrom, since these fibers are very short and thick and are highly con-taminated by two-dimensional q ~ 7~39~
film-like structures.
Finally, it is also known, from Japanese Patent Application 71 41,110, in the name of Kuraray Co., Ltd., published Dece~ber 4, 1971 that fibers are obtained by thorough stirring of a supercooled polyoxymethylene solution. However, this method is too protracted, and is also unsuitable for an industrial process because of its low yield.
The object of the present invention was thus to pro-vide polyoxymethylene fibrids, and a process for their pro-duction, which are free or at least substantially free fromthe disadvantages of the state of the art, and in particular of the abovementioned disadvantages.
The invention thus relates to polyoxymethylene fibrids with a reduced specific viscosity of 0.4 to 2.0 dl x g 1, preferably 0.6 to 1.20 dl x g 1 (measured at 140 C in butyrolactone, which contains 2% by weight of diphenylamine, in a concentration of 0.5 g/100 ml), a specific surface area (measured by the BET method, using argon) of 50 to 200 m2/g, preferably 70 to 110 m2/~, and a freeness (measured by the Schopper-Riegler ~ethod) of 30-80 SR, preferably ~ to 70 SR.
The present invention also relates to a process for the production of polyoxymethylene fibrids by flash-evapor-ation of a superheated solution of the polymer through a nozzle into a low-pressure zone, which comprises using a mix-ture of 50 - 95% by weight o a lower alcohol with 1 - 4 C
atoms and 5 - 50% by weight of water as the solvent.
Suitable materials for the production of the . ~
_ 5_ ~763~
Iibrids ac~ording to the invention are -the kno~m polyoxy-methylenes, By these products there may be understood homopolymers of forrnaldehyde or of a cyclic oligomer of formaldehyde, for example trioxare, the hydroxyl end groups of which have been stabilized chemically, for example by etheri~ication or esterification~ against degradation.
According to the invention, the term polyoxy-methylene also includes copolymers of formaldehyde or o~ a cyclic oligomer of formaldehyde, preferably trioxane, in which, in addition to oxymethylene units, the copoly--mers have, in the main valency chain, oxyalkylene units with at least two, preferably two to eight and in parti-cular two to four, adjacent carbon atoms, and primary alcohol end groups. The comonomer content of the copolymers is appropriately 0.1 to 20 % by weight, pre-~erably 0.-5 to 10 and in particular 0.7 ~ 5 % by weight.
- As compounds which are suitable for copolymeriz-ation with formaldehyde or cyclic oligomers of formalde-hyde, preferably trioxane,there are used, above all, cyclic ethers, preferably with 3, 4 or 5 ring members, and/or cyclic acetals other than -trioxane, preferably .~ormals with 5 to 11, preferably 5, 6 or 7D ring members and/or linear polyace-tals, preferably polyformals.
Suitable comonomers for trioxaneare, in parti-cular, compounds of the formula fH2 ~ , CR H_7X - / 0 ~- (CR H) z_7y -~
in which (A) Rl and R2 are identical or different and .
- 6 - ~ ~ 7~39~
each denote a hydrogen atom, an alipha-tic al~l radical with 1 - 6, preferably 1, 2, 3 or L~, carbon atoms or a phenyl radical and (a) x is 19 2 or 3 and y is zero~ or (b) x is zero, y is 1, 2 or 3 and z is 2, or (c) x is zeroD
y is 1 and z is ~, 4, 5 or 6, or (B) Rl denotes an alkoxy-methyl radical with 2 - 6, preferably 2, 3 or 4, carbon atoms or a phenoxymethyl radical, and wherein x is 1 and y is zero or y and z are 1, and R2 has the abovementioned meaning.
Cyclic ethers which are employed are, above all, epoxides, for example ethylene oxide, propylene oxlde, styrene oxide, cyclohexene oxide, oxacyclobutane and phenyl glycidyl ether.
Suitable cyclic acetals are9 above all, cyclic formals of aliphatic or cycloaliphatic a,~-diols with
By fibrids there are lmderstood small fibers hich are orientated in the longitudinal direction and have a cellulose-like structure, that is to say a finite but non-uniform length, an irregular density, a fissured sur~ace and a high degree of branching. As a result of'their structure, they are particularly suitable, inter alia, for the production of paper.
m e production of such fibrids is described 9 for example, in German Patent Specification 1,290,040. In this procedure, plexus filaments are first produced and are then cut into staple lengths, the staple fiber par-ticles are suspended in a liquid and the particles in suspension are shredded in a manner which is in itself Xnown. In this context, the term plexus filaments relates to a filament-like product of a crystalline plas-tic with a three-dimensional net~rork, which is virtually free from tunnel-like channels and hollow spaces, of numerous molecular orientated ~ilm-like or sliver-like ~ibrids which are less than 2 ~ thick,are combinedwith one another and separate frorn one another along their length at irregular intervals and are preferably orientated in the direc-tion of the longitudinal axis.
These plexus filarnents and their production are described in more detail in Belgian Patent Specification 568,524.To produce theplexus filaments,asolution of a synthetic polymer under il;s autogenous pressure or under a higher pressure is extruded, at a temperature above the boiling point of t~e solvent under normal pressure, through an ~rifice into a chamber which is under a lower pressure This produotion of plexus filaments is also called flash-spiIming or expansion-spinning.
Ple~us filamen-ts can also be prepared from poly-oxymethylene by this route, and then be shredded to ~ibrids. In Belgian Patent Specifica-tion 568,524, aprotic solvents, and in particular methylene chloride, ethylene chloride, acetonitrile and methyl ethyl ketone, are used as solvents for the production of the plexus filaments. As experimen-ts have shown, no fibrids, but exclusively plexus filaments,are formed even at extremely low polymer concentrations, for example of 1 % by weight in methyl ethyl ke-tone. Since plexus filaments are unsuitable for the production of paper, according to -the abovementioned ~erman Patent Specification 1,290,040 they must be processed to fibrids in a second process step, and as a result the process becomes expensive. The :~ polyoxyme-thylene fibrids thus obtained have, in particu-lar, a relatively low specific surface area and a low freeness and the paper produced therefrom is of relatively low strength.
Fibrous products are likewise obtained on preci-pitation of polyoxyme-thylene from its solutions by super-cooling the solution or by discharging into a precipitat-. .
ing agent (compare German Auslegeschrift 1,241,116).However, paper with satisfactory proper-ties cannot be prepared therefrom, since these fibers are very short and thick and are highly con-taminated by two-dimensional q ~ 7~39~
film-like structures.
Finally, it is also known, from Japanese Patent Application 71 41,110, in the name of Kuraray Co., Ltd., published Dece~ber 4, 1971 that fibers are obtained by thorough stirring of a supercooled polyoxymethylene solution. However, this method is too protracted, and is also unsuitable for an industrial process because of its low yield.
The object of the present invention was thus to pro-vide polyoxymethylene fibrids, and a process for their pro-duction, which are free or at least substantially free fromthe disadvantages of the state of the art, and in particular of the abovementioned disadvantages.
The invention thus relates to polyoxymethylene fibrids with a reduced specific viscosity of 0.4 to 2.0 dl x g 1, preferably 0.6 to 1.20 dl x g 1 (measured at 140 C in butyrolactone, which contains 2% by weight of diphenylamine, in a concentration of 0.5 g/100 ml), a specific surface area (measured by the BET method, using argon) of 50 to 200 m2/g, preferably 70 to 110 m2/~, and a freeness (measured by the Schopper-Riegler ~ethod) of 30-80 SR, preferably ~ to 70 SR.
The present invention also relates to a process for the production of polyoxymethylene fibrids by flash-evapor-ation of a superheated solution of the polymer through a nozzle into a low-pressure zone, which comprises using a mix-ture of 50 - 95% by weight o a lower alcohol with 1 - 4 C
atoms and 5 - 50% by weight of water as the solvent.
Suitable materials for the production of the . ~
_ 5_ ~763~
Iibrids ac~ording to the invention are -the kno~m polyoxy-methylenes, By these products there may be understood homopolymers of forrnaldehyde or of a cyclic oligomer of formaldehyde, for example trioxare, the hydroxyl end groups of which have been stabilized chemically, for example by etheri~ication or esterification~ against degradation.
According to the invention, the term polyoxy-methylene also includes copolymers of formaldehyde or o~ a cyclic oligomer of formaldehyde, preferably trioxane, in which, in addition to oxymethylene units, the copoly--mers have, in the main valency chain, oxyalkylene units with at least two, preferably two to eight and in parti-cular two to four, adjacent carbon atoms, and primary alcohol end groups. The comonomer content of the copolymers is appropriately 0.1 to 20 % by weight, pre-~erably 0.-5 to 10 and in particular 0.7 ~ 5 % by weight.
- As compounds which are suitable for copolymeriz-ation with formaldehyde or cyclic oligomers of formalde-hyde, preferably trioxane,there are used, above all, cyclic ethers, preferably with 3, 4 or 5 ring members, and/or cyclic acetals other than -trioxane, preferably .~ormals with 5 to 11, preferably 5, 6 or 7D ring members and/or linear polyace-tals, preferably polyformals.
Suitable comonomers for trioxaneare, in parti-cular, compounds of the formula fH2 ~ , CR H_7X - / 0 ~- (CR H) z_7y -~
in which (A) Rl and R2 are identical or different and .
- 6 - ~ ~ 7~39~
each denote a hydrogen atom, an alipha-tic al~l radical with 1 - 6, preferably 1, 2, 3 or L~, carbon atoms or a phenyl radical and (a) x is 19 2 or 3 and y is zero~ or (b) x is zero, y is 1, 2 or 3 and z is 2, or (c) x is zeroD
y is 1 and z is ~, 4, 5 or 6, or (B) Rl denotes an alkoxy-methyl radical with 2 - 6, preferably 2, 3 or 4, carbon atoms or a phenoxymethyl radical, and wherein x is 1 and y is zero or y and z are 1, and R2 has the abovementioned meaning.
Cyclic ethers which are employed are, above all, epoxides, for example ethylene oxide, propylene oxlde, styrene oxide, cyclohexene oxide, oxacyclobutane and phenyl glycidyl ether.
Suitable cyclic acetals are9 above all, cyclic formals of aliphatic or cycloaliphatic a,~-diols with
2 to 8, preferably 2, 3 or 4~ carbon atoms, the carbon chain of which can be interrupted by an oxygen atom at intervals of 2 carbon atoms, for example glycol formal (1,3-dioxolane), propanediol formal (1,3-dioxane~ butane--diol formal (1,3-dioxepane)and diglycol formal (1,3,6-trioxocane),as well as 4-chloromethyl-1,3-dioxolaneand hexanediol formal (1,3-dioxonane). Unsaturated formals, such as butenediol formal (1,3-d oxacyclohept-5-ene) can also be used.
Suitable linear polyacetals are both homopoly-mers and copolymers of the cyclic acetals defined above~
and linear condensates of aliphatic or cycloaliphatic a,~-diols with aliphatic aldehydes or:thioaldehydes, preferably formaldehyde. ~omopolymers of ]inear for-_ 7~ ~t7~39~
mals of aliphatic ~ diols with 2 - 8, preferably 2 - 4, carbon atomsJ-ror example poly-(1,3-dioxolane), poly-(lp3-dioxane)and poly-(1,3-dioxepane), are used in parti-cular, Compounds with several polymerizable groups in the molecule, for example alkylglycidyl formals, poly-glycol diglycidyl ethers, alkanediol diglycidyl ethers or bis-(alka~etriol) triformals, are op-tionally-also used as additional comonomers for -trioxane, and in parti-cular in an amount of 0.05 to 5 ~ by weight, preferably 0.1 to 2 % by weight, relative to the total amount of monomer, Such additional comonomersare described, for example, in German Auslegeschrift 2,101,817.
The values of the reduced specific viscosity (RSV valuès) of thè polyoxymethylenes employed according to the invention and hence also of the fibrids obtained therefrom are in general between 0 4 and 2,0 dl.g 1, preferably between 0.6 and 1.20 dl-g 1 (measured at 140C in bu-tyrolactone, which contains 2 % by weight of diphenylamine, in a concen-tra-tion of 0.5 g/100 ml).
The crystallite melting points of the polyoxy-methylenes are in the range from 140 to 180C, prefer-ably 150C to 170C, and the densities of the polyoxy-methylenes are between 1.38 and 1.45 g.ml 1, preferably 1.40 and 1.43 g-ml ~ (measured in accordance with the method of DIN 53,479).
.. ..... ......
If polymers with a lower RSV value than that given above are used, fibrids are indeed also formed;
ne~ertheless, they become relatively shor-t and are mixed -7~95 with an increasing am.ount of non-~ibrous consti1;uents.
The length of f.ber and the degree of flneness and of branching of the fibrids can thus be controlled by the RSV ~alue of the polymer, so that the preferred ranges depend on the field of use of the fi~rids, At higher RSV values than that given above~ the danger of the formation of plexus filaments or of predominantly two-dimensional, film-like structures increases.
The oxymethylene copolymers, which are preferably binary or ternary, used according to the invention are prepared in a known manner by polymerizing the monomers in the presence of cat.ionically active catalysts at temperatures between 0 and 100C, preferably between 50 and 90C (compare, for example~ U.S, Patent Specification ~- 15 --3,027,35~ Catalysts which are used in this prepar- -ation are, for example, Lewis acids, for example boron trifluoride and antimony pentafluoride, and complex compounds of Lewis acids, preferably etherates, for example boron trifluoride diethyl etherate and boron trifluoride di-tert,-butyl etherate. Proton acids, for example perchloric acid, and salt-containing com-pounds, for example triphenylmethyl hexafluorophosphate, triethyloxonium tetrafluoborate or acetyl perchlorate, are also suitable. m e polymerization can be carried out in bulk, in suspension or in solution In order to remove unstable constituents, it is expedlent to subjeot the copolymers to controlled partial thermal or hydrolytic degradation until primary alGohol end groups are obtained (compare U.S, Patent Specifications .. - . : ' g ~ ~ ~6395
Suitable linear polyacetals are both homopoly-mers and copolymers of the cyclic acetals defined above~
and linear condensates of aliphatic or cycloaliphatic a,~-diols with aliphatic aldehydes or:thioaldehydes, preferably formaldehyde. ~omopolymers of ]inear for-_ 7~ ~t7~39~
mals of aliphatic ~ diols with 2 - 8, preferably 2 - 4, carbon atomsJ-ror example poly-(1,3-dioxolane), poly-(lp3-dioxane)and poly-(1,3-dioxepane), are used in parti-cular, Compounds with several polymerizable groups in the molecule, for example alkylglycidyl formals, poly-glycol diglycidyl ethers, alkanediol diglycidyl ethers or bis-(alka~etriol) triformals, are op-tionally-also used as additional comonomers for -trioxane, and in parti-cular in an amount of 0.05 to 5 ~ by weight, preferably 0.1 to 2 % by weight, relative to the total amount of monomer, Such additional comonomersare described, for example, in German Auslegeschrift 2,101,817.
The values of the reduced specific viscosity (RSV valuès) of thè polyoxymethylenes employed according to the invention and hence also of the fibrids obtained therefrom are in general between 0 4 and 2,0 dl.g 1, preferably between 0.6 and 1.20 dl-g 1 (measured at 140C in bu-tyrolactone, which contains 2 % by weight of diphenylamine, in a concen-tra-tion of 0.5 g/100 ml).
The crystallite melting points of the polyoxy-methylenes are in the range from 140 to 180C, prefer-ably 150C to 170C, and the densities of the polyoxy-methylenes are between 1.38 and 1.45 g.ml 1, preferably 1.40 and 1.43 g-ml ~ (measured in accordance with the method of DIN 53,479).
.. ..... ......
If polymers with a lower RSV value than that given above are used, fibrids are indeed also formed;
ne~ertheless, they become relatively shor-t and are mixed -7~95 with an increasing am.ount of non-~ibrous consti1;uents.
The length of f.ber and the degree of flneness and of branching of the fibrids can thus be controlled by the RSV ~alue of the polymer, so that the preferred ranges depend on the field of use of the fi~rids, At higher RSV values than that given above~ the danger of the formation of plexus filaments or of predominantly two-dimensional, film-like structures increases.
The oxymethylene copolymers, which are preferably binary or ternary, used according to the invention are prepared in a known manner by polymerizing the monomers in the presence of cat.ionically active catalysts at temperatures between 0 and 100C, preferably between 50 and 90C (compare, for example~ U.S, Patent Specification ~- 15 --3,027,35~ Catalysts which are used in this prepar- -ation are, for example, Lewis acids, for example boron trifluoride and antimony pentafluoride, and complex compounds of Lewis acids, preferably etherates, for example boron trifluoride diethyl etherate and boron trifluoride di-tert,-butyl etherate. Proton acids, for example perchloric acid, and salt-containing com-pounds, for example triphenylmethyl hexafluorophosphate, triethyloxonium tetrafluoborate or acetyl perchlorate, are also suitable. m e polymerization can be carried out in bulk, in suspension or in solution In order to remove unstable constituents, it is expedlent to subjeot the copolymers to controlled partial thermal or hydrolytic degradation until primary alGohol end groups are obtained (compare U.S, Patent Specifications .. - . : ' g ~ ~ ~6395
3,103,49'3 and 3,219,62~.
The homopolymers of formaldehyde or of~ trioxane which are used according -to the invention are likewise prepared in a known manner by catalytic polymerization of the monomer (compare, lor example, U.S Patent Speci-~ications2,768 5 994 and 2,989,505) The fibrids according to the invention are irregular in length, the length in most cases being about 0.1 to 5 mm, preferably 0.2 to 2 mm. The cross-section is likewise irregular in shape and size; the apparent diameter is predominantly about 1 to 200 ~m, preferably 2 to 50 ~m.
Since the fibrids according to the invention are highly branched, they also have a high specific surface ` 15 ''arè'~ '(`measùred`~y`the ~ET me`thod', using` argo'n)'of 50 ' to 200 m2/g, preferably 70 to 110 m2/g, the samples being dried beforehand by freeze-drying. Accordingly, the freeness is also high and is 30 to 80SR9 preferably 40 to 70SR. The freeness is determined as the Schopper-Riegler value in accordance with the method in -Leaflet V/7/61 (old version 107) of the Association of Cellulose and Paper Chemists and Engineers (published on 1st J`uly 1961).
The polyoxymethylene fibrids according to the invention have hydrophilic surface properties and are - therefore readily dispersible in water, in most cases even without wetting agents. Filters produced there-from have improved adsorptive properties. In special cases it may also be expedient to produce hydrophobic - 10_ i~76~95 surface proper-ties by adding sui-table agents l~/hich impart hydrophobic properties, On the basis of their branched morphology, the ~ibrids according -to the invention can very readily be processed to paper in a known manner, for example as described in German Patent Specification 1,290,040.
m e strength properties of these pure polyoxymethylene papers(tensile streng-th, initial wet strength, surface strength, 2-tensile strengh and folding strength) are superior to those of corresponding papers according to the state of -the art~ Thus, the tensile strength of sheets of paper produced from the fibrids according to the invention on. a Rapid-K~then sheet-forming apparatus is 2 to 25 N/mm2, preferably 4 to 20 N/mm2 and in parti-2 -. .: .. ... . .
15 - cular 7 to 17 N/mm , ~neasured with the Instron testing unit with a sheet ~leightof 160 g/m2, a sample width of 15 mm, an elongation rate of 10 mm/minu-te and a measur-. ing length of 100 mm. The measurements are carried out at 23C and a-t a rela-tive humidity of 50 %.
Excellent paperscan also be produced with mix-tures with other fibrous substances, such as cellulose, cellulose fibers and synthetic fibers, and these papers can be glazed, coated, laminated and printed in the customary manner. m e strength properties of these mixed papersare also considerably better than those of comparable papersproduced from kno~n polyoxymethylene fibrids.
~ e POM fibrids accordi.ng to the invention can be employed, for example, for ~allpapers, filters, labels, J 7 ~ ~ ~ 5 graph paper ~nd other specia.l papers and -th~ like. Th polyo~ymethylene ~lbrids can also be processed on card-board-making machines, the resulting cardboard having an .excellent resistance..to water. The polyoxyme-thylene fibrids according to the inventi.on can fur-therrQore be employed in "nonwovens" and can be usecl as thickeners in rapid curing cutback and in dyes, plaster, adhesives, sealing compositions and coating materials based on unsaturated polyesters, epoxide resins, bitumen pastes lQ and PVC plastisols.
The known flash-evaporation of a superhea-ted polymer solution under pressure into a low-pressure zone~
such as is described, for example, in Belgian Patent Specification 568,524, is carriedcut in theprocess, accord-''~`` l5`''i~-g~`t:o~th-e inv`è'ntion9'~or' the`prôduction of the fibrids`.
In this procedure, a solution, which is preferably homogeneoust of the polymer is first prepared, it being possible to use dry or solvent-moist powder or granules~
depending on the manufacturing process, and the polymer being mixed with the solvent and, for example1 being heated in pressure autoclaves, whilst stirring, for example by steam jacket heating or by blowing in steam.
. If, during polymerization or the subsequent stabilizing and working-up process, the polyoxymethylenes are obtained as a solution or suspension in an alcohol/water mixture of the composi-tion according to the invent.ion, it is also possible to employ this solution or suspension directly for the process according to the invention.
According to the invention, as already disclosedt - 12- ~J7~5 a mix-ture of 50 - 95 % by weight of a lower alcohol with 1 - 4 C atoms and 5 - 50 % by weigh-t of water, in each case relative to the total solvent mixture~ is employed as -the solvent Possible lower alcohols ~or this are, 5 for example, methanol, e-thanol, isopropanol, n-propanol, n-butanol, i-butanol or t-butanol, or mixtures of these alcohols. If higher alcohols with more than 4 C atoms, for example n-hexanol, are used, fibrids are indeed also formed, but -the temperature required for the preparation 10 of the solution is then relatively high. Me-thanol and isopropanol are preferably employed The ratio in the mixture'of alcohol and water is of considerable importance for the production of fibrids. For example, if less than 50 % by weight of ''' ~'~`'``'i`5' ~he~lo~er''àl'c'o~ol`and m'oré'`th'an"50 % ~y';wèi''ght 'of'wa:ter '`' are used, plexus filaments are readily formed. Never-theless, this dividing line between the formation of fib-rids and ple~us filaments is not sharp and can also be influenced to a certain extent by the choice of the 20 temperature and of the concentration of the solution and by the choice of the molecular weight and of the dimen-sions of the nozzle and also of the level of the pressure in the expansion zone. With increasing tempera-ture, decreasing polymer concentration and decreasing molecular 25 weight and with an increasin~ length/diameter ratio of the nozzle~and decreasing pressure in the expansion zone, this dividing line shifts somewhat in the direction of -the higher content of water. If more than 95 % of -the lower alcohol and less than 5 % of water are used 9 the _ 13- ~7639~
dissolving temperat;ure required is in most cases ~meconomically hi~ho A mix-ture of 45-10% by weight of water and 55-90 % by weigh-t of lower alcohol i3 preferred.
m e concentration of the polymer in the solven-t mixture is as a rule be-tween 10 and 300 g per liter of solution, pre~erably between 50 and 200 g per liter.
Lower concentrations are as a rule uneconomical since they require a high circulation of solvent; higher con-centrations frequently involve the danger of the form-ation of plexus filamen-ts. m e upper limit of the polymer concentration depends to a certain extent on the molecular weight; the lower the molecular weight, the higher is the permissible concentration.
I5~ The te;mperat~r~iof the~solution~ o~ the polyoxy--~
methylene depends on the molecular weight of the polymer, on the nature and amount o~ comonomer and on the compo-sition of the solvent. If homogeneous solutions are ` used, the lower limit of the temperature is to be regarded as the dissolving temperature which is required, whilst the upper limi-t of the temperature is essentially imposed only by economic considerations. The dissolv ing temperature is known for many examples, and can otherwise easily be interpola-ted from known data or experi-mentally determined by the expert. In any case, thelower limi-t of the temperature must be such tha-t evapor-ation sufficient for -the formation of fibrids takes place in the expansion zone under the chosen pressure conditions. This is as a rule the case if i-t is about ~ ~7639 -- 14 _ 30C above -the boil~ng point under normal pressure and at the same time the solidification point of the polymer is reached. For the preferred alcohols in their preferred ratios in -the mix-ture, the preferred tempera-5 ture range is bet~Yeen 150 and 180C.
The solution is as a rule under the autogenous vapor pressure of the solvent mixture at this temperature, but the pressure can be increased considerably by an inert gas pressure or by a pump. In general, the pres-10 sure is between 15 and 60 bars, preferably between 15and 30 bars.
In addition to the polymers, the solu-tion can also contain auxiliaries from the polymeriza-tion, for example decomposition products of the catalysts for ~?~c~ 15~r~cà~~ polymerizatio~i'tyhich`iare`describéd in Bri~ish'' Patent Specification 1,146,649, in German Offen'egungs-schriften 1, 595,705 and 1, 595,668 and in German Auslege-schriften 1~199~ 504 and 1,175,882, or basic compounds in order to remove unstable constituents until the 20 primary alcohol end group is obtained (for example lower tertiary aliphatic amines, such as triethylamine or tri-ethanolamine, or a secondary alkali metal phospha-te, such as disodiurn hydrogen phosphate (compare U,S, Patent Speci-fications 3,174,948, 3,219,623 and 3,666,714)), and the resulting reaction products, for example methylal, trioxane,tetroxane, forrnic acid and methyl formate.
The polymer solution can also contain the most diverse known additives. Possible additives are~ for example, the customary nucleating agents which accelerate - 15 - ~7639~
crystallization and with the aid of which the morphology of the fibrids can be influenced, such as, for example, branched or crosslinked polyoxymethylenes, talc or boron nitride (compare German Patent Specification 2,101,817 and German Offenlegungsschrift 1,940,132~.
There may also be mentioned in this context the known stabilizers against the influence of heat, oxygen and/or light, such as are described, for example, in German Offenlegungsschrift 2,043,498. Bisphenol compounds, alkaline earth metal salts of carboxylic acids and guanidine compounds are particularly suitable for this. Bisphenol compounds which are used are chiefly esters of monobasic 4-hydroxyphenylalkanoic acids which contain 7-13, preferably 7, 8 or 9, carbon atoms and are monosubstituted or disubstituted on the nucleus by an alkyl radical containing 1 - 4 carbon atoms, with aliphatic dihydric, trihydric or tetrahydric alcohols which contain 2 - 6, preferably 2, 3 or 4, carbon atoms, for example esters of ~-(3-tert.-butyl-4-hydroxy-phenyl)-pentanoic acid,~ -(3-methyl-5-tert.-butyl-4-hydroxy-phenyl)-propionic acid, (3,5-di-tert.-butyl-4-hydroxy-phenyl)-acetic acid,~ -(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionic acid or (3,5-di-isopropyl-4-hydroxy-phenyl)-acetic acid with ethylene glycol,propane-1,2-diol, propane-1,-3-diol, butane-1,4-diol, hexane-1,6-diol, l,l,l-trimethylolethane or pentaerythritol.
Alkaline earth metal salts of carboxylic acids which are used are, in particular, alkaline earth metal salts of aliphatic monobasic, dibasic or tribasic car-.
- 16 - ~763~
boxylic acids which preferably contain hydroxyl groups and have 2 - 20, preferably 3 - 9, carbon atoms, for example the calcium or magnesium salts of stearic acid, ricinoleic acid, lactic acid, mandelic acid, malic acid or citric acid.
Possible guanidine compounds are compounds of the formula NC - NH - C - NH - R
., NH
in which R denotes a hydrogen atom, a cyano group or an 10 alkyl radical with 1 - 6 carbon atoms, for example cyano-guanidine, N-cyano-N'-methylguanidine, N-cyano-Ni-ethyl-guanidine, N-cyano-N'-isopropylguanidine, N-cyano-N'-tert.-butylgu~nidine or N,N'-dicyanoguanidine. The guanidine compound is employed, if appropriate, in an 15 amount of 0.01 - 1% by weight, preferably 0.02 - 0.5%
by weight, relative to the total weight.
Furthermore, the solution can additionally also contain other additives, such as known antistatic agents, flameproofing agents or slip agents or lubricants and the 20 like.
Filled fibrids can be obtained according to the invention by uniformly suspending mineral fillers in the polymer solution and then proceeding as described. Suit-able ~illers are titanium dioxide, calcuim carbonate, 25 talc, wollastonite, dolomite, silicon dioxide and the like.
Dyed polyoxymethylene fibrids can be obtained by dissolving or dispersing dyestuffs in the polymer ~ ~ ~ .
'' , ,' .. . ..
- 17 - ~ ~ 763~ ~
solution. For some applica-tions, the additlon of optical brighteners is also of interest~
Surface--astive agen-ts t such as oxyethylated alcohols, carboxylic acids or amines, alkanesulfonates 5 or polymers carrying hydroxy~L groups, such as polyvinyl alcohol or carboxyrnethylcellulose 7 can also be added to the solution in order to improve the dispersibility of the polyoxymethylene fibrids.
The polymer solution isthen forced through one or morenozzles,the design (size,shapeand length~ of which can indeed influence the dimensions of the fibrids formed and change somewhat the concentration limits given for the solvent mixture, but is not essential to -the invention. Sui-table nozzles are described, for `` ` ~5 example, ln Belgian Pa-tent ~pecification 568,524.
In this con-text there may be mentioned simple nozzles with a diameter o , for example, 0.5 - 5 mm and a length of 0~1 to 1,000 cm, conical nozzles with a com-parable annular gap and two-materlal nozzles, it being possible to use inert gases, such as hydrogen, steam and the like,or liquids, for example superheated water, as the propelling medium.
The polymer solution passes through the nozzle into a zone of lower pressure, in which the solvent is completely or partly evaporated spontaneously. It is also possihle to subject the solution to a controlled pressure release t before its exit from the nozzle, for example by passing it through a chamber or a tube which has a greater diameter than the outlet opening of -the 7639~
nozzle. ~ny residues of the lc)wer alcohol present can be removed, for exarnple, by steam. As a rule, the low-pressure zone is a closed co~-tainer, from which - the solvent vapors are removed wi-th a purnp These vapors can be recycled back, after condensation, into the process. The pressure in the low-pressure zone is between 0.02 bar and 2.0 bars, preferably between 0.1 and 1 bar The fibrids are then freed from most of the sol-vent which has not evaporated off, using known mechanicalmethods, for example by filtration, cen-trifugation and the like, and, if necessary, are washed with wa-ter and then either put to use in moist form or loosened mechanically to ~ density of 10 to 200 g/l, preferably 30 to 100 g/l, and then dried in a stream of hot gas.
A considerable advantage of the process according ~o the invention is that the fibrids are formed directly during atomization and the troublesome and energy-inten-~` sive two-s-~age process, which consists of the production of plexus filaments of infinite length and subsequent mechanical comminution, is thereby avoided. Since -the plexus filaments have a high extensibility, this mechan-ical comminu-tion can be carried out only with a high energy consumption.
This process advantage and the substance advan-- tages of the polyoxymethylene ~ibrids according to the invention could not be predicted and are therefore to be regarded as surprising.
The examples which follow are intended to illus--, - ~ ~76~
tra-te the inven-tion in more detail, Example 1 2 kg of a copolymer which is obtained from 98 ~
by weight of -trloxaneand 2 % by weight of ethylene oxide an~has a RSV value of 0.82 dl/g, and 20 ml of triethylamine are dissolved in a mix-ture of 13 1 of methanol and 7 1 of water at 160C, whilst stirringJ in a pressure vessel which has a volume of 70 1 and is provided with a five-blade multi-stage impeller countercurrent s-tirrer.
An overall pressure of 30 bars is established with the aid of nitrogen, After opening the bottom valve, the solution flows through a single-hole nozzle with a dia-meter of 1 mm and a length of about 0.5 mm into the gas space of a closed collecting tank which has a capacity of 200 1 and is filled with 40 1 of water and in which a vacuum pump ensures a pressure of 0.8 bar. When atomization has ended, methanol is driven off for - 30 minutes by sweeping with steam, the pressure being maintained at 0.8 bar. The fibrid suspension formed is removed through a bottom flap-and centrifuged do~n to a solids content of about 20 %.
In order to determine -the specific surface area of the resulting fibrids, a sample was freeze-dried and measurements were carried out by means of the BET
method, using argon. The specific surface area was 73 m2/g and -the freeness was 50SR, ~ iber classification in a Brecht Holl fiber classification ~it serves as an indirect measure of the fiber leng-th distribution. In this unit, 2 g of ! ~7639~
fibers are washed successively through sieves of differ-ent sizes for lO minutes wi-th the aid of water je-ts under a water pressure of 0.5 ~ar and using a pulsa-ting suction membrane (with as large as possible a stroke).
m e residue on the sieves with mesh widths of 1.2 mm, o.h mm and 0.12 mm and the amount which passes through are given in percent.
m e following fractions were determined in the ~iber classification described above:
Residue 1.2 mm: 0 %
Residue 0.4 mm: 17 %
Residue 0.'12mm: 54 %
Amount passing through 0.12mm: 2g %
Sheets of paper of 160 g/m2 are produced with these fibrids on a Rapid-K~then sheet-forming apparatus.
The tensile strength measured for these sheets was 14.3 N/mm .
Comparison Experiment l As ~escribed in Example l, 2 kg of the same copolymer were dissolved in 20 l of methyl ethyl ketone under the same tempera-ture and pressure conditions and the solution was atomized into the same tank through the same nozzle-l a pressure of 0~8 bar likewise being maintained in the tank. The product formed consisted exclusively o~ continuous plexus filaments which, in this form, were unsuitable for the production of paper, A sample was therefore comminuted by means of a disk refiner, in 6 passes. The following values were found 3 on the fibrids thus produced:
1 ~7~39~
Specific surface area : 39 m2/g Freeness : 27SR
Fiber classification:
Residue 1.2 mm : 3 %
Residue 0.4 mm : 4 %
Residue 0.12 mm : 26 %
Amoun-t passing through 0.12 mm : 67 ~o Tensile strength of the 2 shee~ (160 g/m2) : 0.37 N/mm Plexus filamen-ts which are unsuitable for the production of paper were also obtained when the polymer concentration was reduced to 0~01 kg/l.
Comparison ExPeriment 2 The procedure followed was as in Example 1.
However, -the solvent composi-tion w~s 5 1 of methanol and 15 1 of water. Plexus filaments which, in this form, were unsuitable for the production of paper were exclu-sively formed..
20 Example 2 m e procedure followed was as in Example 1.
However, the RSV value of -the polymer used was 1.0 dl/g and the solvent composition was 15 1 of methanol and ~ 5 1 of water. The following values were measured on 25 the resulting fibrids:
Specific surface area : 98 m2/g Freeness : 61SR
Fiber classification:
Residue 1.2 mm : O %
~0 Resldue 0.4 mm : 5 %
I ~ 7~39~
Residue 0.12 mm: 55 %
Amount passing through 0.12 mm: 40 %
Tensile strength of paper : 13.2 N/~n2 Example ~
The procedure followed was as in Example 1, but isopropanol was used instead of methanol. The following values were measured on the resulting fibrids:
Specific surface area : 108 m2/g Freeness 68SR
Fiber classification:
Residue 1.2 mm. .: 6 %
Residue 0,4 mm 4 %
Residue 0.12 mm: 24 ~0 Amount passing through 0.12 mm: 66 % .
Tensile strength of paper : 11.7 N/m~2 .
.
.
The homopolymers of formaldehyde or of~ trioxane which are used according -to the invention are likewise prepared in a known manner by catalytic polymerization of the monomer (compare, lor example, U.S Patent Speci-~ications2,768 5 994 and 2,989,505) The fibrids according to the invention are irregular in length, the length in most cases being about 0.1 to 5 mm, preferably 0.2 to 2 mm. The cross-section is likewise irregular in shape and size; the apparent diameter is predominantly about 1 to 200 ~m, preferably 2 to 50 ~m.
Since the fibrids according to the invention are highly branched, they also have a high specific surface ` 15 ''arè'~ '(`measùred`~y`the ~ET me`thod', using` argo'n)'of 50 ' to 200 m2/g, preferably 70 to 110 m2/g, the samples being dried beforehand by freeze-drying. Accordingly, the freeness is also high and is 30 to 80SR9 preferably 40 to 70SR. The freeness is determined as the Schopper-Riegler value in accordance with the method in -Leaflet V/7/61 (old version 107) of the Association of Cellulose and Paper Chemists and Engineers (published on 1st J`uly 1961).
The polyoxymethylene fibrids according to the invention have hydrophilic surface properties and are - therefore readily dispersible in water, in most cases even without wetting agents. Filters produced there-from have improved adsorptive properties. In special cases it may also be expedient to produce hydrophobic - 10_ i~76~95 surface proper-ties by adding sui-table agents l~/hich impart hydrophobic properties, On the basis of their branched morphology, the ~ibrids according -to the invention can very readily be processed to paper in a known manner, for example as described in German Patent Specification 1,290,040.
m e strength properties of these pure polyoxymethylene papers(tensile streng-th, initial wet strength, surface strength, 2-tensile strengh and folding strength) are superior to those of corresponding papers according to the state of -the art~ Thus, the tensile strength of sheets of paper produced from the fibrids according to the invention on. a Rapid-K~then sheet-forming apparatus is 2 to 25 N/mm2, preferably 4 to 20 N/mm2 and in parti-2 -. .: .. ... . .
15 - cular 7 to 17 N/mm , ~neasured with the Instron testing unit with a sheet ~leightof 160 g/m2, a sample width of 15 mm, an elongation rate of 10 mm/minu-te and a measur-. ing length of 100 mm. The measurements are carried out at 23C and a-t a rela-tive humidity of 50 %.
Excellent paperscan also be produced with mix-tures with other fibrous substances, such as cellulose, cellulose fibers and synthetic fibers, and these papers can be glazed, coated, laminated and printed in the customary manner. m e strength properties of these mixed papersare also considerably better than those of comparable papersproduced from kno~n polyoxymethylene fibrids.
~ e POM fibrids accordi.ng to the invention can be employed, for example, for ~allpapers, filters, labels, J 7 ~ ~ ~ 5 graph paper ~nd other specia.l papers and -th~ like. Th polyo~ymethylene ~lbrids can also be processed on card-board-making machines, the resulting cardboard having an .excellent resistance..to water. The polyoxyme-thylene fibrids according to the inventi.on can fur-therrQore be employed in "nonwovens" and can be usecl as thickeners in rapid curing cutback and in dyes, plaster, adhesives, sealing compositions and coating materials based on unsaturated polyesters, epoxide resins, bitumen pastes lQ and PVC plastisols.
The known flash-evaporation of a superhea-ted polymer solution under pressure into a low-pressure zone~
such as is described, for example, in Belgian Patent Specification 568,524, is carriedcut in theprocess, accord-''~`` l5`''i~-g~`t:o~th-e inv`è'ntion9'~or' the`prôduction of the fibrids`.
In this procedure, a solution, which is preferably homogeneoust of the polymer is first prepared, it being possible to use dry or solvent-moist powder or granules~
depending on the manufacturing process, and the polymer being mixed with the solvent and, for example1 being heated in pressure autoclaves, whilst stirring, for example by steam jacket heating or by blowing in steam.
. If, during polymerization or the subsequent stabilizing and working-up process, the polyoxymethylenes are obtained as a solution or suspension in an alcohol/water mixture of the composi-tion according to the invent.ion, it is also possible to employ this solution or suspension directly for the process according to the invention.
According to the invention, as already disclosedt - 12- ~J7~5 a mix-ture of 50 - 95 % by weight of a lower alcohol with 1 - 4 C atoms and 5 - 50 % by weigh-t of water, in each case relative to the total solvent mixture~ is employed as -the solvent Possible lower alcohols ~or this are, 5 for example, methanol, e-thanol, isopropanol, n-propanol, n-butanol, i-butanol or t-butanol, or mixtures of these alcohols. If higher alcohols with more than 4 C atoms, for example n-hexanol, are used, fibrids are indeed also formed, but -the temperature required for the preparation 10 of the solution is then relatively high. Me-thanol and isopropanol are preferably employed The ratio in the mixture'of alcohol and water is of considerable importance for the production of fibrids. For example, if less than 50 % by weight of ''' ~'~`'``'i`5' ~he~lo~er''àl'c'o~ol`and m'oré'`th'an"50 % ~y';wèi''ght 'of'wa:ter '`' are used, plexus filaments are readily formed. Never-theless, this dividing line between the formation of fib-rids and ple~us filaments is not sharp and can also be influenced to a certain extent by the choice of the 20 temperature and of the concentration of the solution and by the choice of the molecular weight and of the dimen-sions of the nozzle and also of the level of the pressure in the expansion zone. With increasing tempera-ture, decreasing polymer concentration and decreasing molecular 25 weight and with an increasin~ length/diameter ratio of the nozzle~and decreasing pressure in the expansion zone, this dividing line shifts somewhat in the direction of -the higher content of water. If more than 95 % of -the lower alcohol and less than 5 % of water are used 9 the _ 13- ~7639~
dissolving temperat;ure required is in most cases ~meconomically hi~ho A mix-ture of 45-10% by weight of water and 55-90 % by weigh-t of lower alcohol i3 preferred.
m e concentration of the polymer in the solven-t mixture is as a rule be-tween 10 and 300 g per liter of solution, pre~erably between 50 and 200 g per liter.
Lower concentrations are as a rule uneconomical since they require a high circulation of solvent; higher con-centrations frequently involve the danger of the form-ation of plexus filamen-ts. m e upper limit of the polymer concentration depends to a certain extent on the molecular weight; the lower the molecular weight, the higher is the permissible concentration.
I5~ The te;mperat~r~iof the~solution~ o~ the polyoxy--~
methylene depends on the molecular weight of the polymer, on the nature and amount o~ comonomer and on the compo-sition of the solvent. If homogeneous solutions are ` used, the lower limit of the temperature is to be regarded as the dissolving temperature which is required, whilst the upper limi-t of the temperature is essentially imposed only by economic considerations. The dissolv ing temperature is known for many examples, and can otherwise easily be interpola-ted from known data or experi-mentally determined by the expert. In any case, thelower limi-t of the temperature must be such tha-t evapor-ation sufficient for -the formation of fibrids takes place in the expansion zone under the chosen pressure conditions. This is as a rule the case if i-t is about ~ ~7639 -- 14 _ 30C above -the boil~ng point under normal pressure and at the same time the solidification point of the polymer is reached. For the preferred alcohols in their preferred ratios in -the mix-ture, the preferred tempera-5 ture range is bet~Yeen 150 and 180C.
The solution is as a rule under the autogenous vapor pressure of the solvent mixture at this temperature, but the pressure can be increased considerably by an inert gas pressure or by a pump. In general, the pres-10 sure is between 15 and 60 bars, preferably between 15and 30 bars.
In addition to the polymers, the solu-tion can also contain auxiliaries from the polymeriza-tion, for example decomposition products of the catalysts for ~?~c~ 15~r~cà~~ polymerizatio~i'tyhich`iare`describéd in Bri~ish'' Patent Specification 1,146,649, in German Offen'egungs-schriften 1, 595,705 and 1, 595,668 and in German Auslege-schriften 1~199~ 504 and 1,175,882, or basic compounds in order to remove unstable constituents until the 20 primary alcohol end group is obtained (for example lower tertiary aliphatic amines, such as triethylamine or tri-ethanolamine, or a secondary alkali metal phospha-te, such as disodiurn hydrogen phosphate (compare U,S, Patent Speci-fications 3,174,948, 3,219,623 and 3,666,714)), and the resulting reaction products, for example methylal, trioxane,tetroxane, forrnic acid and methyl formate.
The polymer solution can also contain the most diverse known additives. Possible additives are~ for example, the customary nucleating agents which accelerate - 15 - ~7639~
crystallization and with the aid of which the morphology of the fibrids can be influenced, such as, for example, branched or crosslinked polyoxymethylenes, talc or boron nitride (compare German Patent Specification 2,101,817 and German Offenlegungsschrift 1,940,132~.
There may also be mentioned in this context the known stabilizers against the influence of heat, oxygen and/or light, such as are described, for example, in German Offenlegungsschrift 2,043,498. Bisphenol compounds, alkaline earth metal salts of carboxylic acids and guanidine compounds are particularly suitable for this. Bisphenol compounds which are used are chiefly esters of monobasic 4-hydroxyphenylalkanoic acids which contain 7-13, preferably 7, 8 or 9, carbon atoms and are monosubstituted or disubstituted on the nucleus by an alkyl radical containing 1 - 4 carbon atoms, with aliphatic dihydric, trihydric or tetrahydric alcohols which contain 2 - 6, preferably 2, 3 or 4, carbon atoms, for example esters of ~-(3-tert.-butyl-4-hydroxy-phenyl)-pentanoic acid,~ -(3-methyl-5-tert.-butyl-4-hydroxy-phenyl)-propionic acid, (3,5-di-tert.-butyl-4-hydroxy-phenyl)-acetic acid,~ -(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionic acid or (3,5-di-isopropyl-4-hydroxy-phenyl)-acetic acid with ethylene glycol,propane-1,2-diol, propane-1,-3-diol, butane-1,4-diol, hexane-1,6-diol, l,l,l-trimethylolethane or pentaerythritol.
Alkaline earth metal salts of carboxylic acids which are used are, in particular, alkaline earth metal salts of aliphatic monobasic, dibasic or tribasic car-.
- 16 - ~763~
boxylic acids which preferably contain hydroxyl groups and have 2 - 20, preferably 3 - 9, carbon atoms, for example the calcium or magnesium salts of stearic acid, ricinoleic acid, lactic acid, mandelic acid, malic acid or citric acid.
Possible guanidine compounds are compounds of the formula NC - NH - C - NH - R
., NH
in which R denotes a hydrogen atom, a cyano group or an 10 alkyl radical with 1 - 6 carbon atoms, for example cyano-guanidine, N-cyano-N'-methylguanidine, N-cyano-Ni-ethyl-guanidine, N-cyano-N'-isopropylguanidine, N-cyano-N'-tert.-butylgu~nidine or N,N'-dicyanoguanidine. The guanidine compound is employed, if appropriate, in an 15 amount of 0.01 - 1% by weight, preferably 0.02 - 0.5%
by weight, relative to the total weight.
Furthermore, the solution can additionally also contain other additives, such as known antistatic agents, flameproofing agents or slip agents or lubricants and the 20 like.
Filled fibrids can be obtained according to the invention by uniformly suspending mineral fillers in the polymer solution and then proceeding as described. Suit-able ~illers are titanium dioxide, calcuim carbonate, 25 talc, wollastonite, dolomite, silicon dioxide and the like.
Dyed polyoxymethylene fibrids can be obtained by dissolving or dispersing dyestuffs in the polymer ~ ~ ~ .
'' , ,' .. . ..
- 17 - ~ ~ 763~ ~
solution. For some applica-tions, the additlon of optical brighteners is also of interest~
Surface--astive agen-ts t such as oxyethylated alcohols, carboxylic acids or amines, alkanesulfonates 5 or polymers carrying hydroxy~L groups, such as polyvinyl alcohol or carboxyrnethylcellulose 7 can also be added to the solution in order to improve the dispersibility of the polyoxymethylene fibrids.
The polymer solution isthen forced through one or morenozzles,the design (size,shapeand length~ of which can indeed influence the dimensions of the fibrids formed and change somewhat the concentration limits given for the solvent mixture, but is not essential to -the invention. Sui-table nozzles are described, for `` ` ~5 example, ln Belgian Pa-tent ~pecification 568,524.
In this con-text there may be mentioned simple nozzles with a diameter o , for example, 0.5 - 5 mm and a length of 0~1 to 1,000 cm, conical nozzles with a com-parable annular gap and two-materlal nozzles, it being possible to use inert gases, such as hydrogen, steam and the like,or liquids, for example superheated water, as the propelling medium.
The polymer solution passes through the nozzle into a zone of lower pressure, in which the solvent is completely or partly evaporated spontaneously. It is also possihle to subject the solution to a controlled pressure release t before its exit from the nozzle, for example by passing it through a chamber or a tube which has a greater diameter than the outlet opening of -the 7639~
nozzle. ~ny residues of the lc)wer alcohol present can be removed, for exarnple, by steam. As a rule, the low-pressure zone is a closed co~-tainer, from which - the solvent vapors are removed wi-th a purnp These vapors can be recycled back, after condensation, into the process. The pressure in the low-pressure zone is between 0.02 bar and 2.0 bars, preferably between 0.1 and 1 bar The fibrids are then freed from most of the sol-vent which has not evaporated off, using known mechanicalmethods, for example by filtration, cen-trifugation and the like, and, if necessary, are washed with wa-ter and then either put to use in moist form or loosened mechanically to ~ density of 10 to 200 g/l, preferably 30 to 100 g/l, and then dried in a stream of hot gas.
A considerable advantage of the process according ~o the invention is that the fibrids are formed directly during atomization and the troublesome and energy-inten-~` sive two-s-~age process, which consists of the production of plexus filaments of infinite length and subsequent mechanical comminution, is thereby avoided. Since -the plexus filaments have a high extensibility, this mechan-ical comminu-tion can be carried out only with a high energy consumption.
This process advantage and the substance advan-- tages of the polyoxymethylene ~ibrids according to the invention could not be predicted and are therefore to be regarded as surprising.
The examples which follow are intended to illus--, - ~ ~76~
tra-te the inven-tion in more detail, Example 1 2 kg of a copolymer which is obtained from 98 ~
by weight of -trloxaneand 2 % by weight of ethylene oxide an~has a RSV value of 0.82 dl/g, and 20 ml of triethylamine are dissolved in a mix-ture of 13 1 of methanol and 7 1 of water at 160C, whilst stirringJ in a pressure vessel which has a volume of 70 1 and is provided with a five-blade multi-stage impeller countercurrent s-tirrer.
An overall pressure of 30 bars is established with the aid of nitrogen, After opening the bottom valve, the solution flows through a single-hole nozzle with a dia-meter of 1 mm and a length of about 0.5 mm into the gas space of a closed collecting tank which has a capacity of 200 1 and is filled with 40 1 of water and in which a vacuum pump ensures a pressure of 0.8 bar. When atomization has ended, methanol is driven off for - 30 minutes by sweeping with steam, the pressure being maintained at 0.8 bar. The fibrid suspension formed is removed through a bottom flap-and centrifuged do~n to a solids content of about 20 %.
In order to determine -the specific surface area of the resulting fibrids, a sample was freeze-dried and measurements were carried out by means of the BET
method, using argon. The specific surface area was 73 m2/g and -the freeness was 50SR, ~ iber classification in a Brecht Holl fiber classification ~it serves as an indirect measure of the fiber leng-th distribution. In this unit, 2 g of ! ~7639~
fibers are washed successively through sieves of differ-ent sizes for lO minutes wi-th the aid of water je-ts under a water pressure of 0.5 ~ar and using a pulsa-ting suction membrane (with as large as possible a stroke).
m e residue on the sieves with mesh widths of 1.2 mm, o.h mm and 0.12 mm and the amount which passes through are given in percent.
m e following fractions were determined in the ~iber classification described above:
Residue 1.2 mm: 0 %
Residue 0.4 mm: 17 %
Residue 0.'12mm: 54 %
Amount passing through 0.12mm: 2g %
Sheets of paper of 160 g/m2 are produced with these fibrids on a Rapid-K~then sheet-forming apparatus.
The tensile strength measured for these sheets was 14.3 N/mm .
Comparison Experiment l As ~escribed in Example l, 2 kg of the same copolymer were dissolved in 20 l of methyl ethyl ketone under the same tempera-ture and pressure conditions and the solution was atomized into the same tank through the same nozzle-l a pressure of 0~8 bar likewise being maintained in the tank. The product formed consisted exclusively o~ continuous plexus filaments which, in this form, were unsuitable for the production of paper, A sample was therefore comminuted by means of a disk refiner, in 6 passes. The following values were found 3 on the fibrids thus produced:
1 ~7~39~
Specific surface area : 39 m2/g Freeness : 27SR
Fiber classification:
Residue 1.2 mm : 3 %
Residue 0.4 mm : 4 %
Residue 0.12 mm : 26 %
Amoun-t passing through 0.12 mm : 67 ~o Tensile strength of the 2 shee~ (160 g/m2) : 0.37 N/mm Plexus filamen-ts which are unsuitable for the production of paper were also obtained when the polymer concentration was reduced to 0~01 kg/l.
Comparison ExPeriment 2 The procedure followed was as in Example 1.
However, -the solvent composi-tion w~s 5 1 of methanol and 15 1 of water. Plexus filaments which, in this form, were unsuitable for the production of paper were exclu-sively formed..
20 Example 2 m e procedure followed was as in Example 1.
However, the RSV value of -the polymer used was 1.0 dl/g and the solvent composition was 15 1 of methanol and ~ 5 1 of water. The following values were measured on 25 the resulting fibrids:
Specific surface area : 98 m2/g Freeness : 61SR
Fiber classification:
Residue 1.2 mm : O %
~0 Resldue 0.4 mm : 5 %
I ~ 7~39~
Residue 0.12 mm: 55 %
Amount passing through 0.12 mm: 40 %
Tensile strength of paper : 13.2 N/~n2 Example ~
The procedure followed was as in Example 1, but isopropanol was used instead of methanol. The following values were measured on the resulting fibrids:
Specific surface area : 108 m2/g Freeness 68SR
Fiber classification:
Residue 1.2 mm. .: 6 %
Residue 0,4 mm 4 %
Residue 0.12 mm: 24 ~0 Amount passing through 0.12 mm: 66 % .
Tensile strength of paper : 11.7 N/m~2 .
.
.
Claims (11)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polyoxymethylene fibrid having a reduced specific viscosity of 0.4 to 2.0 dl/g-1, a specific surface area of 50 to 200 m2/g and a freeness of 30 to 80°SR.
2. A polyoxymethylene fibrid as claimed in claim 1 in which the specific surface area is 70 to 110 m2/g.
3. A polyoxymethylene fibrid as claimed in claim 1 in which the freeness is between 40 and 70°SR.
4. A polyoxymethylene fibrid as claimed in claim 1, claim 2 or claim 3 in which the polyoxymethylene is a homopolymer of formaldehyde.
5. A polyoxymethylene fibrid as claimed in claim 1, claim 2 or claim 3 in which the polyoxymethylene is a homopolymer of a cyclic oligomer of formaldehyde.
6. A polyoxymethylene fibrid as claimed in claim 1, claim 2 or claim 3 in which the polyoxymethylene is a copolymer of formaldehyde or of a cyclic oligomer thereof with at least one member of the group of cyclic ethers, cyclic acetals, linear acetals and mixtures thereof.
7. A process for the production of a polyoxymethylene fibrid by flash-evaporation of a superheated solution of the polymer in a solvent through a nozzle into a low-pressure zone, which comprises using a mixture of 50 - 95 % by weight of a lower alcohol with 1 - 4 carbon atoms and 5 to 50 % by weight of water as solvent.
8. A process as claimed in claim 7 in which the alcohol is methanol or isopropanol.
9. A process as claimed in claim 7 or claim 8 in which the solvent is a mixture of 55 - 90 % by weight of the alcohol and 10 - 45 % by weight of water.
10. A paper comprising polyoxymethylene fibrids as claimed in claim 1.
11. A paper as claimed in claim 10 in which the fibrids are admixed with at least one other fibrous substance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2947490.6 | 1979-11-24 | ||
| DE19792947490 DE2947490A1 (en) | 1979-11-24 | 1979-11-24 | POLYOXYMETHYLENE FIBRIDE AND METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1176395A true CA1176395A (en) | 1984-10-16 |
Family
ID=6086845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000365227A Expired CA1176395A (en) | 1979-11-24 | 1980-11-21 | Polyoxymethylene fibrids, a process for their production and their use |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4493751A (en) |
| EP (1) | EP0029572B1 (en) |
| JP (1) | JPS56134212A (en) |
| AT (1) | ATE7933T1 (en) |
| CA (1) | CA1176395A (en) |
| DE (2) | DE2947490A1 (en) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3144916A1 (en) * | 1981-11-12 | 1983-05-19 | Hoechst Ag, 6230 Frankfurt | POLYOXYMETHYLENE FIBRIDE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| EP0176316A3 (en) * | 1984-09-18 | 1989-04-26 | Toa Nenryo Kogyo Kabushiki Kaisha | A process for the production of a non woven fabric of water soluble resin fibres |
| US4929502A (en) * | 1986-10-14 | 1990-05-29 | American Cyanamid Company | Fibrillated fibers and articles made therefrom |
| JPH0759615B2 (en) * | 1986-11-14 | 1995-06-28 | 三菱瓦斯化学株式会社 | Improved stabilization method for polyoxymethylene copolymers |
| US5090975A (en) * | 1990-09-21 | 1992-02-25 | The Drackett Company | High efficiency vacuum cleaner bags |
| US5482773A (en) * | 1991-07-01 | 1996-01-09 | E. I. Du Pont De Nemours And Company | Activated carbon-containing fibrids |
| FR2689530B1 (en) * | 1992-04-07 | 1996-12-13 | Aussedat Rey | NEW COMPLEX PRODUCT BASED ON FIBERS AND FILLERS, AND METHOD FOR MANUFACTURING SUCH A NEW PRODUCT. |
| US5250237A (en) * | 1992-05-11 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Alcohol-based spin liquids for flash-spinning polymeric plexifilaments |
| DE4441801C1 (en) * | 1994-11-24 | 1996-06-05 | Messer Griesheim Gmbh | Polyesterfibride |
| JP3771008B2 (en) * | 1997-07-16 | 2006-04-26 | ポリプラスチックス株式会社 | Process for producing branched or cross-linked polyacetal resin |
| DE19925491A1 (en) | 1999-06-04 | 2000-12-14 | Ticona Gmbh | Polyoxymethylene molded parts with improved resistance to diesel fuel and aggressive gasoline |
| DE19943178A1 (en) | 1999-09-09 | 2001-03-15 | Ticona Gmbh | Polyoxymethylene with improved stability against acids and its use |
| DE10029533A1 (en) | 2000-06-15 | 2001-12-20 | Ticona Gmbh | Polyoxymethylene thermoplastic molding composition, useful for producing articles having sliding contact with hard surfaces, comprises polyoxyethylene homo- or co-polymer and a polyethylene wax lubricant |
| DE10237884A1 (en) | 2002-08-19 | 2004-03-11 | Ticona Gmbh | Impact-resistant polyoxymethylene molding compositions, their use and molded articles made therefrom |
| CN100537860C (en) * | 2003-04-03 | 2009-09-09 | 纳幕尔杜邦公司 | Form the method for uniformly distributed material |
| EP1704184A1 (en) | 2003-12-18 | 2006-09-27 | Ticona GmbH | Polyoxymethylene molding compounds and use thereof |
| DE10361230A1 (en) * | 2003-12-24 | 2005-07-28 | Ticona Gmbh | Composite body, process for its preparation and its use |
| DE102004024061A1 (en) * | 2004-05-13 | 2005-12-08 | Ticona Gmbh | Process for the preparation of polyacetal plastic composites and apparatus suitable therefor |
| DE102004036757A1 (en) * | 2004-07-29 | 2006-03-23 | Bayer Materialscience Ag | Cyclic oligoformals in polycarbonate |
| DE102004047200B4 (en) * | 2004-09-29 | 2010-06-02 | Ticona Gmbh | Composite of polyacetal and thermoplastic vulcanizate elastomer |
| DE102005001373A1 (en) | 2005-01-12 | 2006-07-27 | Ticona Gmbh | Polyoxymethylene fibers, process for their preparation and their use |
| US7410696B2 (en) | 2005-01-12 | 2008-08-12 | Ticona Gmbh | Polyoxymethylene fibers, production thereof and use thereof |
| US7915350B2 (en) | 2005-04-15 | 2011-03-29 | Ticona Gmbh | Polyoxymethylene compositions, their preparation and use |
| US8008390B2 (en) | 2005-09-16 | 2011-08-30 | Ticona Gmbh | Polyoxymethylene molding compositions, their use, and moldings produced therefrom |
| US20070114034A1 (en) * | 2005-11-18 | 2007-05-24 | Chevron U.S.A. Inc. | Controlling pressure and static charge build up within an annular volume of a wellbore |
| JPWO2008069184A1 (en) * | 2006-12-04 | 2010-03-18 | 三菱瓦斯化学株式会社 | Oxymethylene copolymer composition for stretched material, stretched material, structure and production method thereof |
| DE102008018966A1 (en) | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Process for the preparation of oxymethylene polymers and apparatus suitable therefor |
| DE102008018965A1 (en) | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Oxymethylene copolymers and their use, as well as processes for the preparation of oxymethylene copolymers |
| DE102008018968A1 (en) | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Polyoxymethylene molding compounds and molded articles and their use |
| DE102008018967A1 (en) | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Oxymethylene polymers, process for their preparation and their use |
| DE102008055840B4 (en) | 2008-11-04 | 2013-04-18 | Ticona Gmbh | Polyoxymethylene composition, process for producing a granule and use |
| US8840976B2 (en) | 2010-10-14 | 2014-09-23 | Ticona Llc | VOC or compressed gas containment device made from a polyoxymethylene polymer |
| EP2652038A1 (en) | 2010-10-14 | 2013-10-23 | Ticona GmbH | Plasticized polyoxymethylene |
| CN108485175A (en) | 2010-10-14 | 2018-09-04 | 塞拉尼斯销售德国有限公司 | The polyformaldehyde of glass fiber reinforcement |
| EP2652001B1 (en) | 2010-10-14 | 2018-12-26 | Celanese Sales Germany GmbH | Coupled glass-fiber reinforced polyoxymethylene |
| EP2505609B1 (en) | 2011-04-01 | 2015-01-21 | Ticona GmbH | High impact resistant polyoxymethylene for extrusion blow molding |
| EP2581408B1 (en) | 2011-10-14 | 2015-07-29 | Ticona GmbH | Tribologically modified glass-fiber reinforced polyoxymethylene |
| WO2013101624A1 (en) | 2011-12-30 | 2013-07-04 | Ticona Llc | Printable molded articles made from a polyoxymethylene polymer composition |
| EP2647666A1 (en) | 2012-04-05 | 2013-10-09 | Ticona GmbH | Tribologically modified polyoxymethylene |
| EP2653497B1 (en) | 2012-04-17 | 2015-01-28 | Ticona GmbH | Weather resistant polyoxymethylene compositions |
| WO2014097270A1 (en) | 2012-12-20 | 2014-06-26 | Ticona Gmbh | Fiber reinforced polyoxymethylene composition with improved thermal properties |
| EP2938674A1 (en) | 2012-12-27 | 2015-11-04 | Ticona LLC | Impact modified polyoxymethylene composition and articles made therefrom that are stable when exposed to ultraviolet light |
| WO2017056064A1 (en) | 2015-09-30 | 2017-04-06 | Celanese Sales Germany Gmbh | Low friction squeak free assembly |
| US11015031B2 (en) | 2017-06-16 | 2021-05-25 | Celanese Sales Germany Gmbh | Reinforced polyoxymethylene composition with low emissions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK116229B (en) * | 1957-06-11 | 1969-12-22 | Du Pont | Continuously extruded or spun filament product and process for its manufacture. |
| NL246230A (en) * | 1958-12-09 | |||
| JPS5136809B2 (en) * | 1972-07-03 | 1976-10-12 | ||
| CA1032328A (en) * | 1972-08-30 | 1978-06-06 | Crown Zellerbach International | Process for making discrete fibers by flashing a polymer solution having water dispersed therein |
| DE2346081C2 (en) * | 1973-09-13 | 1982-06-03 | Basf Ag, 6700 Ludwigshafen | Process for the production of aqueous suspensions from short polyolefin fibers |
-
1979
- 1979-11-24 DE DE19792947490 patent/DE2947490A1/en not_active Withdrawn
-
1980
- 1980-11-18 AT AT80107133T patent/ATE7933T1/en not_active IP Right Cessation
- 1980-11-18 EP EP80107133A patent/EP0029572B1/en not_active Expired
- 1980-11-18 DE DE8080107133T patent/DE3068248D1/en not_active Expired
- 1980-11-21 JP JP16345980A patent/JPS56134212A/en active Granted
- 1980-11-21 CA CA000365227A patent/CA1176395A/en not_active Expired
-
1982
- 1982-09-09 US US06/416,154 patent/US4493751A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE2947490A1 (en) | 1981-06-04 |
| EP0029572B1 (en) | 1984-06-13 |
| DE3068248D1 (en) | 1984-07-19 |
| JPH0157166B2 (en) | 1989-12-04 |
| ATE7933T1 (en) | 1984-06-15 |
| EP0029572A1 (en) | 1981-06-03 |
| US4493751A (en) | 1985-01-15 |
| JPS56134212A (en) | 1981-10-20 |
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